Aniline azo dyes from 1,2,3,4-tetrahydroquinoline and 2,3-dihydro-1,4-benzoxazine couplers containing sulfate alkyl groups

ABSTRACT

Disclosed are novel dyes which comprise aniline diazo moieties and certain aromatic amine couplers having sulfate groups. These dyes are substantially water soluble and are particularly useful for dyeing polyamide, wool and the like and exhibit, for example, excellent dyeability properties and fastness to light and gas. The dyes correspond to the general formula: ##STR1## wherein ring A may be unsubstituted or substituted with 1-3 of a variety of groups which themselves may be substituted such as alkyl, alkoxy, chloro, bromo, iodo, trifluoromethyl, thiocyano, cyano, phenylazo, acyl, and the like; R 1  is a group such as alkyl, alkoxy, halogen, acylamido, alkylthio, and aryloxy; m is 0, 1, or 2; R 2  represents the linking groups necessary to form a 1,2,3,4-tetrahydroquinoline or a 2,3-dihydro-1,4-benzoxazine structure, which may be substituted, in combination with the phenylene ring; Z is a linking group such as alkylene; and M is H + , Na + , K + , or NH 4   + .

This invention concerns novel dyes which comprise aniline diazo moietiesand certain aromatic amine couplers having sulfate groups. These dyesare substantially water soluble and are particularly useful for dyeingpolyamide, wool and the like and exhibit, for example, excellentdyeability properties and fastness to light and gas.

The dyes of this invention correspond to the following general formula:##STR2## wherein ring A may be unsubstituted or substituted with 1-3groups selected from alkyl, alkoxy, chloro, bromo, iodo,trifluoromethyl, thiocyano, cyano, phenylazo, acyl, aroyl, carbamoyl,sulfamoyl, alkylsulfonyl, alkenylsulfonyl, arylsulfonyl, alkylthio,arylthio, aryloxy, alkoxycarbonyl, arylamido, aryloxycarbonyl,COO-alkylene-X, CONH-alkylene-X, ##STR3## SO₂ NH-alkylene-X, ##STR4##SO₂ -alkylene-X, SO₂ N(alkyl)₂, ##STR5## SO₂ O-aryl, formyl, and NHSO₂-alkyl, wherein X is one or more groups selected from hydrogen, hydroxy,halogen, aryl, cycloalkyl, alkoxy, aryloxy, acylamido, cyano,alkoxyalkoxy, acyloxy, succinimido, alkylsulfonomido, 2-pyrrolidino,alkylthio, and arylthio; R₁ is selected from alkyl, alkoxy, halogen,acylamido, alkylthio, and aryloxy; m is 0, 1, or 2; R₂ represents thelinking groups necessary to form a 1,2,3,4-tetrahydroquinoline or a2,3-dihydro-1,4-benzoxazine structure in combination with the phenylenering; Z is a linking group such as alkylene; and M is H⁺, Na⁺, K⁺, orNH₄ ⁺. The aliphatic portions of the various alkyl, alkylene, alkenyl,alkoxy, alkanoyl and the like groups throughout this specification, arestraight or branched chain of 1-6 carbons and the types and degrees ofsubstitutions thereof and also of the cyclic moieties as further definedbelow must, of course, be judiciously selected.

The couplers are described more particularly by the following formulae:##STR6## wherein

R₁ is selected from hydrogen, alkyl, alkoxy, halogen, acylamido,alkylthio, and aryloxy;

R₃, R₄ and R₅ are each selected from hydrogen and alkyl; m is 0, 1 or 2;M is Na⁺, K⁺, H⁺ or NH₄ ⁺ ; and Z is alkylene, or --CH₂ (CH₂)_(n) X--CH₂(CH₂)_(p) --, where n is 1, 2 or 3, p is 0, 1, 2 or 3, and X is O, S,SO₂, --SO₂ NH--, --SO₂ N(alkyl)--, SO₂ N(aryl), --N(SO₂ aryl)--,--NHCO--, --NHCONH, --N(SO₂ alkyl), or --CON(alkyl).

All of the aforesaid "aliphatic portions" of the various alkyl, etc.,groups and the various aromatic and alicyclic radicals may besubstituted, for example, with up to three of aryl, phenyl, halogen,OSO₃ M, alkoxy, aryloxy, hydroxy, cyclohexyl, furyl, alkylcyclohexyl,aroyloxy, alkoxycarbonyl, alkanoyloxy, sulfamoyl, SO₂ NH(aryl), SO₂NH(alkyl), SO₂ N(dialkyl), NHCOO(alkyl), NHCONH(alkyl), acylamido,alkylsulfonamido, succinimido, glutarimido, phthalimido, 2-pyrrolidono,cyano, carbamoyl, alkylcarbamoyl, alkoxyalkoxy, alkylthio, arylthio,alkylsulfonyl or arylsulfonyl.

The dyes of this invention impart orange to blue shades on fibers,particularly polyamides, and are especially useful for dyeing polyamide(nylon) carpets, giving good fastness to light, ozone, oxides ofnitrogen, washing, sublimation, crocking, and the like, and having goodleveling, transfer, depth of shade, exhaustion and build properties.

The substituted anilines used in this invention are prepared accordingto known procedures. The dyes may be prepared as follows:

Method I: An intermediate coupler containing one or more hydroxy groupsmay be reacted with sulfuric acid to produce a sulfate ester, which isthen coupled with a diazonium salt to give the dye, as follows: ##STR7##

Method II: An intermediate coupler containing one or more hydroxy groupsmay be coupled with the diazonium salt and then the dye reacted withsulfuric acid to produce the sulfate ester, as follows: ##STR8## Thedyes may be isolated when M is H⁺, but are usually isolated as thesodium or potassium salts. The following examples will furtherillustrate these preparative methods.

COUPLER PREPARATIONS Example 1 Preparation of2,7-Dimethyl-N-(2,3-disulfatopropyl)1,2,3,4-tetrahydroquinoline

To 40 g. of concentrated sulfuric acid is added 11.75 g. ofN-(2,3-dihyroxypropyl)-2,7-dimethyl-1,2,3,4-tetrahydroquinoline at about50° C. The material is difficult to dissolve and requires stirring forseveral hours at room temperature. After solution is completed, stirringis continued for 1 hr.

Example 2 Preparation ofN-(2-Sulfatoethyl)-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline

To 250 ml of concentrated sulfuric acid is added 120 g. ofN-(2-hydroxyethyl)-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline atless than 30° C. The solution is stirred for 2 hrs. and drowned onto1250 g. of ice and water. After stirring for about 30 min., the whitesolid which precipitates is collected by filtration, washed with 10%sodium chloride solution, and dried at 60° C.

Example 3 Preparation ofN-(2-Sulfatoethyl)-1,2,3,4-tetrahydro-2,2,4-trimethylquinoline

N-(2-Hydroxyethyl)-1,2,3,4-tetrahydro-2,2,4-trimethylquinoline (110 g.)is treated exactly as in Example 2 to yield the sulfate product which isa white solid.

Example 4 Preparation ofN-(2-Sulfatoethyl)-2,3-dihydro-3,6-dimethyl-1,4-benzoxazine

N-(2-Hydroxyethyl)-2,3-dihydro-3,6-dimethyl-1,4-benzoxaine (25 g.) isadded at about 30° C. to concentrated sulfuric acid (50 ml). Aftersolution is complete, stirring is continued for 1 hr. and the reactionsolution drowned in ice-water to produce a total volume of about 500 ml.The coupler solution is used without further treatment.

The following are typical coupler types bearing hydroxy groups which maybe treated in a similar manner as described above to produce sulfategroups. ##STR9##

PREPARATION OF THE DYES--METHOD I Examples 5-9

To 25 ml of concentrated H₂ SO₄ is added 3.6 g. of NaNO₂ portionwisebelow 80° C. The solution is cooled and 50 ml of 1:5 acid (1 partpropionic acid; 5 parts acetic acid) is added below 20° C. To themixture is added 2-chloro-4-methylsulfonylaniline (10.28 g., 0.05 m)followed by 50 ml 1:5 acid, all at 0°-5° C. The reaction mixture isstirred at 0°-5° C. for 2 hrs. Each of the couplers (0.01 m) listedbelow is Examples 5-9 is added to water, or a 0.01 m aliquot of thecoupler in dilute H₂ SO₄ is added to water and cooled in an ice bath.

To each chilled coupler is added a 0.01 mole aliquot of the diazoniumsolution. The coupling mixture is treated with enough potassium acetateto neutralize the mineral acid. Water is added to the coupling mixtureto a total volume of about 200 ml and the dyes coolected by filtration,washed with 10% KCl solution, and dried in air. The dyes usually areadmixed with about an equal weight of K₂ SO₄ and are used for dyeingwithout further purification to produce red shades on polyamides.

    ______________________________________                                        EXAMPLE NO.                                                                   ______________________________________                                        5          N-(2-Sulfatoethyl)-1,2,3,4-tetrahydro-2,2,4-                                  trimethylquinoline                                                 6          N-(2-Sulfatoethyl)-1,2,3,4-tetrahydro-2,2,4,7-                                tetramethylquinoline                                               7          N-(2-Sulfatoethyl)-2,7-dimethyl-1,2,3,4-                                      tetrahydroquinoline                                                8          2,3-Dihydro-3,6-dimethyl-N-(2-sulfatoethyl)-                                  1,4-benzoxazine                                                    9          2,3-Dihydro-3-methyl-N-(2-sulfatoethyl)-                                      1,4-benzoxazine                                                    ______________________________________                                    

PREPARATION OF DYES--METHOD II Example 10 Reaction of Hydroxy-ContainingDye With Sulfuric Acid and Sodium Hydroxide ##STR10##

To 15 ml of concentrated H₂ SO₄ is added 2.5 g of Dye I portionwise andstirring continued for 30 min. at about 30° C. The solution is added to75 g of ice with stirring. The dye is collected by filtration. The wetfilter cake is stirred in 150 ml of water and pH is adjusted to about 13by addition of 50% NaOH solution. The sodium salt of the dye is thencollected by filtration, washed with saturated NaCl solution, and driedby heating at 60° C. The dye produces a bright yellowish red shade whendyed on nylon carpet. The dyes in the following tables are prepared in asimilar manner. In the talbes in the (R₁)_(m) column, the word "none"means --H.

                                      TABLE I                                     __________________________________________________________________________     ##STR11##                                                                    Substituents on                                                               Ring A        (R.sub.1).sub.m                                                                         R.sub.3                                                                          R.sub.4                                                                             R.sub.5                                                                          Z                  M                      __________________________________________________________________________    2-Cl          None      CH.sub.3                                                                         CH.sub.3                                                                            CH.sub.3                                                                         CH.sub.2 CH.sub.2  K.sup.+                2-CH.sub.35-Cl                                                                              "         H  CH.sub.3                                                                            "  "                  "                      2,5-di-CH.sub.3                                                                             7-CH.sub.3                                                                              "  "     H  "                  "                      2-CN4-SO.sub.2 CH.sub.3                                                                     "         CH.sub.3                                                                         "     "  "                  "                      2,4-di-SO.sub.2 CH.sub.3                                                                    7-CH.sub.3                                                                              H  CH(CH.sub.3).sub.2                                                                  "  "                  "                      4-SO.sub.2 OC.sub.6 H.sub.5                                                                 7-OCH.sub.3                                                                             "  CH.sub.3                                                                            "  "                  "                      2-COC.sub.4 H.sub.5                                                                         5-OCH.sub.3, 8-CH.sub.3                                                                 "  "     "  "                  "                      2-CO.sub.2 C.sub.4 H.sub.5                                                                  5,8-di-OCH.sub.3                                                                        "  "     CH.sub.3                                                                         "                  "                      4-SO.sub.2 CH.sub.3                                                                         5,8-di-CH.sub.3                                                                         "  "     "  "                  "                      2,6-di-Cl4-SO.sub.2 CH.sub.3                                                                7-Cl      "  "     "  "                  "                      2-CN4-Cl      5,8-diCl  "  "     "  "                  "                      2-CN5-Cl      None      "  "     "  "                  Na.sup.+               4-COCH.sub.3  5-OCH.sub.3, 8-CH.sub.3                                                                 CH.sub.3                                                                         "     "  "                  "                      4-CN          7-NHCHO   "  "     "  "                  "                      4-CHO         7-NHCOCH.sub.3                                                                          "  "     H  "                  "                       ##STR12##    7-NHCOCH.sub.2 OCH.sub.3                                                                "  "     "  "                  "                      2-CN4-SO.sub.2 NH.sub.2                                                                     7-NHCOOC.sub.2 H.sub.5                                                                  "  "     "  "                  "                      2-CN4-COCH.sub.3                                                                            7-NHCOC.sub.6 H.sub.5                                                                   "  "     "  "                  "                      2-CN4-COOC.sub.2 H.sub.5                                                                    7-NHCONHC.sub.2 H.sub.5                                                                 "  "     "  "                  K.sup.+                2-CN4-SCN     7-NHCOC.sub.6 H.sub.11                                                                  "  "     CH.sub.3                                                                         "                  "                      2-COOCH.sub.34-SCN                                                                          None      "  "     "  "                  "                      2,4-di-CN     7-CH.sub. 3                                                                             H  "     "  "                  "                      2,4,6-tri-CN  "         "  H     "  "                  "                      2,6-di-CN     "         "  CH.sub.3                                                                            "  "                  "                      2-Br4-SO.sub.2 NHC.sub.3 H.sub.6 OCH.sub.3                                                  "         "  "     "  "                  "                      4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                         "         "  "     "  "                  "                      4-CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 CN                                              "         "  "     H  "                  "                      4-SO.sub.2 NHC.sub.2 H.sub.4 NHCOCH.sub.3                                                   "         "  "     "  "                  "                       ##STR13##    7-OCH.sub. 3                                                                            "  "     "  "                  "                       ##STR14##    7-CH.sub. 3                                                                             "  "     "  "                  "                      2-SC.sub.6 H.sub.54-CN                                                                      "         "  "     "  "                  "                      2-OC.sub.6 H.sub.54-Cl                                                                      "         "  "     "  "                  "                      4-NHCOCH.sub.3                                                                              "         "  "     "  "                  "                      2-CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3                                             "         "  "     "  "                  "                      2-COOCH.sub.34-SO.sub.2 CH.sub.3                                                            "         "  "     "  "                  "                      2-SCH.sub.34-Cl                                                                             None      "  "     "  "                  "                      2-CN4-CONH.sub.2                                                                            "         "  "     "  "                  "                      2-CONHC.sub.2 H.sub.4 OH4-Cl                                                                "         "  "     "  "                  "                      2-CO.sub.2 CH.sub.34,6-di-Br                                                                "         "  "     CH.sub.3                                                                         "                  "                       ##STR15##    7-CH.sub. 3                                                                             "  "     "  "                  "                      4-SO.sub.2 NHC.sub.2 H.sub.4 NHCOCH.sub.3                                                   "         "  "     "  "                  "                      4-SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.4 OH                                                    "         "  "     "  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                             "                      2,6-di-CN4-SO.sub.2 CH.sub.3                                                                "         "  "     "  CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                             "                      2,6-di-CN4-Cl "         "  "     H  CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                           CH.sub.2           "                      2,6-di-CN4-CHO                                                                              "         "  "     "  CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)                                        CH.sub.2 CH.sub.2  "                      2-Cl4-SO.sub.2 CH.sub.3                                                                     "         "  "     "  CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2                                         CH.sub.2           "                      "             "         "  "     "  CH.sub.2 CH.sub.2 CH.sub.2                                                    NHCOCH.sub.2       "                      "             "         "  "     "  CH.sub.2 CH.sub.2 CONHCH.sub.2                                                CH.sub.2           "                      "             "         "  "     "  CH.sub.2 CH.sub.2 N(COC.sub.6                                                 H.sub.5)CH.sub.2 CH.sub.2                                                                        "                      "             "         "  "     "  CH.sub.2 CH(CH.sub.3)                                                                            "                      "             "         "  "     "  CH.sub.2 CH(OSO.sub.3 Na)CH.sub.2                                                                Na.sup.+               "             "         "  "     "  CH.sub.2 CH(CH.sub.2 Cl)                                                                         "                      "             "         "  "     "  CH.sub.2 CH(CH.sub.2 OCH.sub.3)                                                                  "                      "             "         "  "     "  CH.sub.2 CH(C.sub.6 H.sub.5)                                                                     "                      "             "         "  "     "  CH.sub.2 CH(CH.sub.2 OC.sub.6                                                                    ".sub.5)               "             "         "  "     "  CH.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3)                                        SO.sub.2 CH.sub.2 CH.sub.2                                                                       "                      "             "         "  "     "  CH.sub.2 CH.sub.2 CH.sub.2                                                                       "                      __________________________________________________________________________

    __________________________________________________________________________     ##STR16##                                                                    Substituents on                                                               Ring A         (R.sub.1).sub.m                                                                         R.sub.3                                                                           Z                  M                             __________________________________________________________________________    4-Cl           None      H   CH.sub.2 CH.sub.2  Na.sup.+                      2,5-di-Cl      6-CH.sub.3                                                                              "   "                  "                             2,5-di-CH.sub.3                                                                              "         CH.sub.3                                                                          "                  "                             2-CN4-SO.sub.2 CH.sub.3                                                                      6-OCH.sub. 3                                                                            "   "                  "                             4-SO.sub.2 C.sub.2 H.sub.5                                                                   "         H   "                  "                             2,6-di-Cl4-SO.sub.2 CH.sub.3                                                                 6-CH.sub. 3                                                                             CH.sub.3                                                                          CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                                              "                             2-CN4-Cl       "         "   CH.sub.2 CH.sub.2  "                             2-SO.sub.2 C.sub.6 H.sub.5                                                                   "         "   "                  "                             4-COCH.sub.3   "         "   "                  "                             2-COOCH.sub.3  "         "   "                  "                             2-COOCH.sub.34-Cl                                                                            "         "   "                  "                             2-CONHC.sub.2 H.sub.5                                                                        "         "   "                  "                             2-Br4-CONH.sub.2                                                                             "         "   "                  "                             2-CN4-COCH.sub.3                                                                             "         "   "                  "                             2-CN4-COOC.sub.2 H.sub.5                                                                     6-NHCOCH.sub.3                                                                          "   "                  K.sup.+                       2-COOCH.sub.34-SCN                                                                           6-NHCOC.sub.6 H.sub.5                                                                   "   "                  "                             2-CN4-SCN2-COOCH.sub.3                                                                       6-NHCOC.sub.4 H.sub.5n                                                                  "   "                  "                             4-SO.sub.2 NH.sub.2                                                                          6-NHCONHC.sub.2 H.sub.5                                                                 "   "                  "                             2-Cl5-SO.sub.2 NHC.sub.2 H.sub.4 OH                                                          6-NHCOCH.sub.2 OCH.sub.3                                                                "   "                  "                             4-SO.sub.2 OC.sub.6 H.sub.5                                                                  6-NHCOCH.sub.2 CN                                                                       "   "                  "                             2-Br4-SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                      6-CH.sub. 3                                                                             "   "                  Na.sup.+                       ##STR17##     "         "   "                  "                             4-NHCOCH.sub.3 "         "   "                  "                             2,4-di-CN      "         "   "                  "                             2,4,6-tri-CN   "         "   "                  "                             2,6-di-CN      "         "   "                  "                             4-COOC.sub.2 H.sub.4 OH                                                                      "         "   "                  "                             4-COOC.sub.3 H.sub.6 OCH.sub.3                                                               "         "   "                  "                             4-SO.sub.2 NHCH.sub.2 CH(OH)CH.sub.2 OH                                                      "         "   "                  "                              ##STR18##     6-NHCHO   "   "                  "                             4-CO.sub.2 C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                 6-CH.sub.3                                                                              "   "                  "                             2-CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                 "         "   "                  "                             2-CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                "         "   "                  "                             4-SO.sub.2 CH.sub.2 CHCH.sub.2                                                               "         "   "                  "                             2-SC.sub.4 H.sub.9n-4-Cl                                                                     "         "   "                  "                             2-SC.sub.2 H.sub.54-CN                                                                       "         "   "                  "                             2-OC.sub.6 H.sub.54-COCH.sub.3                                                               "         "   "                  "                              ##STR19##     "         "   "                  "                             2-OCH.sub.34-Cl6-CN                                                                          "         "   CH.sub.2 CH(CH.sub.3)                                                                            "                             4-COOC.sub.6 H.sub.11                                                                        "         "   CH.sub.2 CH(C.sub.6 H.sub.5)                                                                     "                             4-COOC.sub.6 H.sub.5                                                                         "         "   CH.sub.2 CH(CH.sub.2 Cl)                                                                         "                             2,6-di-CN5-CHO "         "   CH.sub.2 CH(OSO.sub.3 K)CH.sub.2                                                                 "                             2,6-di-CN4-CH.sub.3                                                                          "         "   CH.sub.2 CH(CH.sub.2 OC.sub.6 H.sub.5)                                                           "                             2-Cl4-SO.sub.2 CH.sub.3                                                                      "         "   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                             "                             "              "         "   CH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2                                                             "                             "              "         "   CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2                                                     "                             "              "         "   CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)CH.sub.                                 2 CH.sub.2         "                             "              "         "   CH.sub.2 CH.sub.2 N(SO.sub.2 C.sub.6                                          H.sub.5)CH.sub.2 CH.sub.2                                                                        "                             "              "         "   CH.sub.2 CH.sub.2 SO.sub.2 N(CH.sub.3)CH.sub.                                 2 CH.sub.2         "                             "              "         "   CH.sub.2 CH.sub.2 NHCOCH.sub.2                                                                   "                             "              "         "   CH.sub.2 CH.sub.2 CH.sub.2 NHSO.sub.2                                         CH.sub.2 CH.sub.2  "                             "              "         "   CH.sub.2 CH.sub.2 CONHCH.sub.2 CH.sub.2                                                          "                             "              "         "   CH.sub.2 CH.sub.2 CONHCH.sub.2 CH.sub.2                                       CH.sub.2 CH.sub.2  "                             "              "         "   CH.sub.2 CH.sub.2 SO.sub.2 N(C.sub.6                                          H.sub.5)CH.sub.2 CH.sub.2                                                                        "                             "              "         "   CH.sub.2 CH.sub.2 NHCONHCH.sub.2 CH.sub.2                                                        "                             "              "         "   CH.sub.2 CH.sub.2 CH.sub.2                                                                       "                             2,4-di-CH.sub.3 SO.sub.2                                                                     "         "   CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2SCH.sub.2                                  CH.sub.2           "                             __________________________________________________________________________

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

We claim:
 1. The dye of the formula: ##STR20## wherein ring A isunsubstituted or substituted with 1-3 groups selected from alkyl,alkoxy, chloro, bromo, iodo, trifluoromethyl, thiocyano, cyano,phenylazo, alkanoyl, aroyl, carbamoyl, sulfamoyl, alkylsulfonyl,alkenylsulfonyl, arylsulfonyl, alkylthio, arylthio, aryloxy,alkoxycarbonyl, arylamido, aryloxycarbonyl, COO-alkylene-X,CONH-alkylene-X, ##STR21## SO₂ NH-alkylene-X, ##STR22## SO₂ -alkylene-X,SO₂ N(alkyl)₂, ##STR23## SO₂ O-aryl, formyl, and NHSO₂ -alkyl, wherein Xis one or more groups selected from hydrogen, hydroxy, halogen, aryl,cycloalkyl, alkoxy, aryloxy, alkanoylamino, cyano, alkoxyalkoxy,alkanoyloxy, succinimido, alkylsulfonamido, 2-pyrrolidino, alkylthio andarylthio; and wherein the coupler C has the formula: ##STR24## whereinR₁ is selected from hydrogen, alkyl, alkoxy, halogen, alkanoylamino,alkylthio, and aryloxy;R₃, R₄ and R₅ are each selected from hydrogen andalkyl; Z is alkylene or --CH₂ (CH₂)_(n) X-CH₂ (CH₂)_(p) --, where n is1, 2 or 3, p is 0, 1, 2 or 3, and X is O, S, SO₂, --SO₂ NH--, --SO₂N(alkyl)--, SO₂ N(aryl)--, --N(SO₂ aryl)--, --NHCO--, --NHCONH--,--N(SO₂ alkyl)--, or --CON(alkyl)--; M is H⁺, Na⁺, K⁺ or NH₄ ⁺ ; m is 0,1 or 2; wherein the alkyl, alkoxy, alkanoyl and aryl substituents of R₁,R₃, R₄, R₅, and Z are unsubstituted or substituted with up to three ofthe following groups: aryl, halogen, OSO₃ M, alkoxy, aryloxy, hydroxy,cyclohexyl, furyl, alkylcyclohexyl, aroyloxy, alkoxycarbonyl,alkanoyloxy, sulfamoyl, SO₂ NH(aryl), SO₂ NH(alkyl), SO₂ N(dialkyl),NHCOO(alkyl), NHCONH(alkyl), alkanoylamino, alkylsulfonamido,succinimido, glutarimido, phthalimido, 2-pyrrolidono, cyano, carbamoyl,alkylcarbamoyl, alkoxyalkoxy, alkylthio, arylthio, alkylsulfonyl orarylsulfonyl; wherein each of the alkyl, alkylene and alkenyl portionsof the above groups contain 1-6 carbons, and is straight or branchedchain.
 2. The compound according to claim 1 of the formula ##STR25## 3.The compound according to claim 1 of the formula ##STR26##
 4. Thecompound according to claim 1 of the formula ##STR27##
 5. The compoundaccording to claim 1 of the formula ##STR28##
 6. The compound accordingto claim 1 of the formula ##STR29##